Method for Producing a Latent Heat Storage Material and Dialkyl Ether as a Latent Heat Storage Material

ABSTRACT

The invention relates to a method for producing latent heat storage material from linear alcohols by dehydrating to dialkyl ethers or to olefins, and hydrating to paraffins and dialkyl ether as a latent heat storage material.

FIELD OF THE INVENTION

The invention relates to a method for producing a latent heat storagematerial from linear alcohols and dialkyl ether as a latent heat storagematerial.

BACKGROUND OF THE INVENTION

Phase change materials (PCMs) may release or absorb, respectively, orstore, respectively, heat by melting or solidifying, respectively,within a defined temperature range, and thus function as latent heatstorage materials. This principle of heat storage may also be used, forexample, in the wall insulation of buildings. Such latent heat storagematerials are, e.g. in the form of micro-capsules, introduced into thewall plaster or into gypsum plasterboards and liquefy during the daywith high heat input. The heat absorbed is stored in the wall and keepsthe interior cool. Following cooling during the evening hours and atnight, the liquid storages solidify and release the crystallization heatto the environment. In that, the interior is warmed up.

As latent heat storage materials, predominantly paraffins and paraffinmixtures are used. Commercially available paraffin mixtures for PCMapplications are, for example, Rubitherm® 27 and Rubitherm® 31. The maincomponent of the above Rubitherm® mixtures is C₁₈ paraffin with acontent of only 59 or 39% by mass, respectively. These paraffin mixturesconsist of even- and odd-numbered linear paraffins in the chain lengthrange of C₁₇ to C₂₁ or C₁₇ to approx. C₃₀, respectively, however, have aportion of linear chains of 98.0 or 95.6% by mass, respectively.

Paraffins may also be produced by hydrating commercially availablealpha-olefins. These, however, only have linearities of approx. 90 toless than 95% by mass in the C₁₆ to C₁₈ range, and have the disadvantagethat due to the branched side products, their melting enthalpy isclearly lower in comparison to that of highly linear paraffins.

It was found, that mixtures of even-numbered and odd-numbered paraffins,such with different chain lengths and/or higher branched portions havethe disadvantage that these have wide or several different meltingpeaks, wherein, when these peaks are too far apart with regard to thetemperature, normally only part of the possible melting enthalpy canactually be used.

SUMMARY OF THE INVENTION

The object of the present invention therefore is the provision of highlylinear compounds, like paraffins, with a defined chain length for use aslatent heat storage materials. Herewith, the following advantages areachieved: on the one hand, the melting range of highly pure paraffins isclearly narrower compared to paraffin mixtures, and thus the fullstorage capacity can be used at low temperature differences already. Onthe other hand, the melting enthalpy of the pure substance is clearlyhigher than that of the mixtures.

The invention is defined by the subject matter of the independentclaims. Preferred embodiments are the subject matter of the dependentclaims or described hereinafter.

DESCRIPTION OF PREFERRED EMBODIMENT

Pure substances, in particular linear paraffins with defined chainlengths, have higher melting heats and narrower melting ranges thanbranched paraffins or paraffin mixtures. Via the selection of thestructure and chain length of the paraffin, the melting temperature ofthe PCM can be set across a wide temperature range.

The paraffins preferably fulfill the following specification independentfrom each other:

-   a) they have even-numbered chain lengths at more than 95 by mass, in    particular more than 98 by mass,-   b) they exclusively have a certain C-number at more than 95% by    mass, in particular more than 97% by mass,-   c) they are linear at more than 95% by mass.

The dialkyl ethers respectively have two residues R, so that the limitvalues are respectively lower. The dialkyl ethers preferably fulfill thefollowing specification independent from each other:

-   a) they have even-numbered chain lengths at more than 91% by mass,    in particular more than 95% by mass,-   b) they exclusively have a certain C-number at more than 91% by    mass, in particular more than 94% by mass, and-   c) they are linear at more than 91% by mass, in particular more than    95% by mass.

In particular, the alcohols are purified or selected, respectively, suchthat they already fulfill the above limit values for the paraffins, forproducing the dialkyl ethers as well as for producing the paraffins.

The latent heat storage material is obtainable by dehydrating linearfatty alcohols to dialkyl ethers or to olefins, wherein the latter aresubsequently hydrated to paraffins. Fatty alcohols in terms of thisinvention are alcohols with C-numbers higher than or equal to 6 andpreferably with terminal hydroxy groups. Particularly suitable startingmaterials in case of the paraffins are cetyl alcohol or stearyl alcohol,and in case of the dialkyl ethers lauryl alcohol or myristyl alcohol.

It was thus surprisingly found that particularly paraffins are suited aslinear paraffins for PCM applications, which can be produced bydehydrating linear alcohols to linear olefins and their subsequenthydration. The linear alcohols used are easily available as singlesections and are preferably based on renewable vegetable or animal rawmaterials, in particular vegetable ones, like e.g. palm oil, palm kerneloil, coconut oil, rapeseed oil or other vegetable oils.

Alcohols obtainable from natural raw materials are characterized by anincreased linearity of e.g. >98% by mass. The paraffins producedtherefrom are therefore surprisingly well suited for application inPCMs. Beside native sources for the alcohols, ethylene oligomerisationaccording to the Ziegler synthesis, too, is a source for the alcoholsused according to the invention.

Alternatively, paraffins may also be used, which can be produced bydehydrating synthetic alcohols. In the chain length range C₁₆ to C₁₈,however, normally these frequently only have linearities from 93 to 99%.

The use of linear paraffins as PCMs is known, just like the productionof paraffins from fatty alcohols. So far, however, no paraffins havebeen described for this application as latent heat storage material,which are produced from dehydrated alcohols, in particular such ones,which are available from renewable raw materials.

In the past, the skilled person always assumed that the production ofalcohols from paraffins is a refinement step, in which the alcohol has ahigher value than the paraffin. Now, it was not to be expected that thereverse path, i.e. the production of paraffin from an alcohol, iseconomically reasonable. However, it was now demonstrated that paraffinsfrom alcohol dehydration result in particularly pure paraffins, and thatthese pure paraffins have clearly better characteristics, even comparedto only slightly contaminated paraffins.

For this special application, the prices of the paraffins are higherthan the prices of fatty alcohols. The required quantities of latentheat storage used directly correlate with the melting heat used, i.e.that substances which have a 20% higher melting heat, also accordinglyhave to be used in lesser quantities in order to achieve the sameeffect. For example, textiles can be produced with the same storagecapacity with a lesser weight, and thus the wearing comfort can beclearly increased.

A further dehydration product of linear fatty alcohols are dialkylethers. These are likewise very non-polar and are characterized by sharpmelting peaks and a high melting heat. In particular didodecyl ether andditetradecyl ether have similar melting temperatures like e.g. C₁₈ orC₂₂ paraffins, respectively. Suitable catalysts for the dehydration todialkyl ethers are clays, including boehmitic clays.

In the comparison of products produced by means of dehydrating fattyalcohol, dialkyl ethers and olefins/paraffins, the dialkyl ethers havethe advantage that they can be produced economically, since for every 2mol of fatty alcohol, only 1 mol of water has to be eliminated. As faras desired, the ethers may be stabilized against peroxide formation bymeans of antioxidants, wherein it is assumed, that in the micro- ormacro-capsules, in which PCMs are frequently used, a decomposition ofthe ethers is sufficiently minimized by the capsule layer (frequently apolymer layer).

The latent heat storage material is preferably encapsulated by a polymermaterial as the capsule wall in micro-capsules with average particlesizes in the range from 1 to 200 μm, or in macro-capsules with averageparticle sizes in the range of more than 200 μm to 2 cm. Suitablepolymer materials are, e.g., styrene divinylbenzene polymers orunsaturated polyesters. Preferred wall materials, since they are veryresistant to ageing, particularly are thermoset polymers. Suitablethermoset polymer materials are, for example, cross-linked formaldehyderesins, cross-linked polyureas and cross-linked polyurethanes as well ascross-linked methacrylic acid ester polymers.

Melting temperature and melting heat are determined by means of DSCanalytics. With a defined heating and cooling rate, the onsettemperature (melting temperature) and the area below the curve (meltingheat) are determined. The melting temperatures and heats of theparaffins and paraffin mixtures determined by means of DSC arerespectively represented in the experiment part.

The Figures Show:

FIG. 1 C-chain distribution, of paraffins Rubitherm® 27 and Rubitherm®31;

FIG. 2 DSC diagram of C16 to C22 paraffins (pure);

FIG. 3 DSC diagram for comparison of Rubitherm® 31/Di-C12 ether/C20paraffin;

FIG. 4 DSC diagram for comparison of Rubitherm® 27/C18 paraffin/C16paraffin;

FIG. 5 DSC diagram Di-C12/C14/C16/C18 ethers, and

FIG. 6 DSC diagram for comparison of hexadecane from a synthetic/nativesource.

EXPERIMENT PART

The evaluation of the DSC analyses for the determination of meltingenthalpy [J/g] and onset temperature was performed according to DIN53765. All DSC curves were measured with the device DSC 204 F1 of thecompany Netzsch with heating and cooling rates of 10 K/min.

Comparative Example

Commercially available PCMs are Rubitherm® 27 and Rubitherm® 31:Rubitherm® 27 and Rubitherm® 31 have the composition as apparent fromFIG. 1 (determined via GC) and furthermore show the followingcharacteristic determined via DSC:

TABLE 1 Paraffin Rubitherm ® 27 Rubitherm ® 31 n-paraffin content [%]98.0 95.6 Onset 1 [° C.] 4 −2 Onset 2 [° C.] 26 27 Melting heat 1 [J/g]22.0 17.9 Melting heat 2 [J/g] 156.3 147.8

As an example for dehydrating linear fatty alcohols, the dehydration ofhexadecanol to linear olefins (Experiment 1) and the hydration ofhexadecene (Experiment 2) are described in the following.

Experiment 1

Dehydrating fatty alcohols to linear olefins 2474 g of NACOL® 16-99(purity 99.5%, based on renewable raw materials) were mixed with 500 gof Al₂O₃ and 60 ml of xylene in a 6 l flask and heated at up to 295° C.at the water separator for 4.5 hours. In that, 180 ml of water wereformed. The hexadecene formed was distilled in vacuum. The yield was amixture of alpha- and internal olefins.

Experiment 2

Hydrating linear olefins to linear paraffins 685 g of the hexadeceneobtained in Experiment 1 were hydrated for 7 hours at 98° C. accordingto a known method over a heterogeneous Ni-containing catalyst at 20 barH₂ pressure and filtrated after cooling.

Fatty alcohols with chain lengths of C₁₆ to C₂₂ were used according toExperiments 1 and 2, and the following paraffins were obtained:

TABLE 2 Paraffin Hexadecane Octadecane Eicosane Docosane n-paraffin(main 99.6 98.8 93.2 97.4 component) [%] n-paraffin 99.8 98.9 96.8 98.6(total) [%] iso-paraffin [%] 0.2 0.1 1.8 1.2 Onset [° C.] 17.4 27.4 32.540.6 Melting heat [J/g] 245.6 250.7 247.2 270.5

Experiment 3

Experiments 1 and 2 were repeated, however, a synthetic fatty alcohol(hexadecanol) from the Ziegler process with a purity of 95.6% was usedas the alcohol.

Experiment 4

Experiment 2 was repeated, however, a synthetic olefin (hexadecene exChevron Phillips) with a purity of 94.2% was used as the olefin.

A comparison of the onset temperatures and melting heats for paraffinsof different purity due to different production methods are compiled inthe following table for hexadecane by way of example.

TABLE 3 Paraffin Hexadecane Hexadecane Hexadecane Test number 1 2 3Source Native alcohol Synth. alcohol Synth. olefin n-C₁₆ paraffin [%]99.6 91.8 92.3 n-paraffin (total) [%] 99.8 93.1 93.2 iso-paraffin(total) [%] 0.2 6.3 6.2 Onset [° C.] 17.4 13.6 14.3 Melting heat [J/g]245.6 224.2 207.8

Experiment 5-7

Octadecane and Docosane were mixed at weight ratios of 1:1, 2:1, and3:1, and the DSC curves were measured again.

TABLE 4 Paraffin mixture [weight ratio] C₁₈/C₂₂ paraffin C₁₈/C₂₂paraffin C₁₈/C₂₂ paraffin 1:1 2:1 3:1 Onset 1 [° C.] −1.6 −1.2 −0.5Onset 2 [° C.] 28.5 26.6 26.7 Melting 17.67 21.64 19.93 heat 1 [J/g]Melting 123.9 128.7 123.4 heat 2 [J/g]

As an example for the partial dehydration of linear fatty alcohols, thedehydration of dodecanol to linear dialkyl ethers is described in thefollowing.

Experiment 8-11: Dehydrating linear fatty alcohols dialkyl ethers

10 kg/h of NACOL® 12-99 (purity 99.2%, based on renewable raw materials)were led over Al₂O₃ beads in a fixed bed reactor (Ø=60 mm, l=900 mm) at260° C. according to a known method. The didodecyl ether formed wassubsequently distilled in vacuum.

TABLE 5 Dialkyl ether Didodecyl Ditetradecyl Dihexadecyl Dioctadecylether ether ether ether Purity [%] 93.4 95.2 94.8 91.2 Onset [° C.] 30.441.8 51.5 59.3 Melting heat [J/g] 209.4 227.4 231.2 207.9

1-17. (canceled)
 18. New. A method for absorbing heat by liquefying alatent heat storage material and emitting the heat stored in the latentheat storage material following cooling by solidifying, by using alatent heat storage material produced from linear fatty alcohols,comprising dehydrating linear fatty alcohols, wherein more than 95% bymass of the fatty alcohols used are linear, to produce; (a) olefins,wherein the olefins are hydrated to paraffins, the paraffins comprisingexclusively a certain C-number at more than 95% by mass, or (b) dialkylethers of the formula R₁—O—R₂, wherein R₁ and R₂, independent of oneanother, are hydrocarbon residues with 6 to 22 carbon atoms, whereinmore than 95% by mass of the sum of all residues R₁ and R₂ comprise thesame C-number, and the residues R₁ and R₂ are equal.
 19. New. The methodaccording to claim 18, characterized in that said paraffins compriseeven-numbered chain lengths at more than 95% by mass.
 20. New. Themethod according to claim 18, characterized in that said paraffinsexclusively comprise a certain C-number at more than 97% by mass. 21.New. The method according to claim 18, characterized in that saiddialkyl ethers comprise even-numbered chain lengths at more than 91% bymass.
 22. New. The method according to claim 18, characterized in thatsaid dialkyl ethers exclusively comprise a certain C-number at more than94% by mass.
 23. New. The method according to claim 18, characterized inthat said fatty alcohols, in the case of the producing olefins are cetylalcohol or stearyl alcohol, and in case of producing dialkyl esters arelauryl alcohol or myristyl alcohol.
 24. New. The method according toclaim 18, characterized in that said fatty alcohols are obtained fromnative vegetable raw materials.
 25. New. The method according to claim18, characterized in that said fatty alcohols are produced by ethyleneoligomerisation according to the Ziegler synthesis.
 26. New. The methodaccording to claim 18, characterized in that one or more of said latentheat storage materials are encapsulated by a polymer material as thecapsule wall into micro-capsules with average particle sizes in therange from 1 to 200 um, or into macro-capsules with average particlesizes in the range from more than 200 um to 2 cm.
 27. New. A method forstoring heat by liquefying and emitting heat by solidifying as in alatent heat storage material comprising using as said latent heatstorage material dialkyl ethers of the formula R₁—O—R₂, wherein R₁ andR₂, independent of one another, are hydrocarbon residues with 6 to 22carbon atoms, and wherein more than 95% by mass of the sum of allresidues R₁ and R₂ are linear, more than 95% by mass of the sum of allresidues R₁ and R₂ have the same C-number, and the residues R₁ and R₂are equal.
 28. New. The method according to claim 27, characterized inthat more than 98% by mass of the sum of all residues R₁ and R₂ arelinear.
 29. New. The method according to claim 27, characterized in thatmore than 95% by mass, of the sum of all residues R₁ and R₂ areeven-numbered.
 30. New. The method according to claim 27, characterizedin that more than 97% by mass of the sum of all residues R₁ and R₂comprise the same C-number.
 31. New. The method according to claim 27,characterized in that said dialkyl ethers are derived from the hydrationof fatty alcohols, in particular lauryl alcohol or myristyl alcohol. 32.New. The method according to claim 31, characterized in that fattyalcohols are obtained from native vegetable raw materials.
 33. New. Themethod according to claim 27, characterized in that said latent heatstorage material is encapsulated by a polymer material as the capsulewall into micro-capsules with average particle sizes in the range from 1to 200 um, or into macro-capsules with average particle sizes in therange from more than 200 um to 2 cm.
 34. New. The method according toclaim 24, comprising dehydrating said fatty alcohols to produce saidalcohols having at least one of the following characteristics: more than95% by mass of said alcohols are linear or the alcohols compriseeven-numbered chain lengths at more than 95% by mass; or the alcoholscomprises a certain C-number at more than 97% by mass.